Aliphatic nitraza polynitro compounds



United States Patent 3 000 956 ALIPHATIC NITRAZA PdLYNlTRO COMPOUNDS Milton B. Frankel, Pasadena, Calif., assignor to Aerojetfigural Corporation, Aznsa, Califl, a corporation of o No Drawing. Filed Oct. 28, 1957, Ser. No. 694,692 20 Claims. (Cl. 260-583) This invention relates to new compositions of matter and a method for their preparation. In particular, this invention relates to bis-mineral acid salts of aliphatic nitraza polynitro diamincs having the general formula:

1 L I or Jo and to their corresponding free diamines; wherein X is an anion of a strong mineral acid, theA radicals are alkylene radicals which may be the same or difierent, and n is a small whole number from 1 to 3, inclusive.

The diamines of the present invention condense with fl-geminal polynitro alcohols, such as 2,2,2-trinitroethanol, to form nitramine compounds, as more fully disclosed in assignee's copending US. patent application Serial No. 451,705, filed August 23, 1954, now abandoned. The'nitramine compounds thus formed react with nitric acid to yield high energy nitramincs, as more fully disclosed in assignees oopending US. patent application Serial No. 641,437, filed February 19, 1957.

The high energy nitramines prepared from the diamines of this invention by the method described above are useful as high explosives and can be used in any conventional explosive missile,projectile, rocket, or the like, as the main explosive charge. An example of such a missile is disclosed in United States Patent No. 2,470,- 162, issued May 17, 1249. One way of using the high explosives in a'device such as that disclosed in United States Patent No. 2,470,162 is to pack the crystalline explosive' in powder form into the warhead of the-missile. Alternatively, the crystals can be first pelletized and then packed. A charge thus prepared is sufiiciently insensitive to withstand the shock entained in the ejectionof a shell from a gun barrel ,or from a rocket launching tube under the pressure developed from ignition of a pro pellant charge, and can be caused to explode'on operadetonating explosive such as lead azide or mercury tulminate.

The novel inorganic acid salts of the present invention, are prepared by reacting an aliphatic'nitraza polynitro Patented Sept. 19, 196E EXAMPLE Preparation of the bis-nitric acid salt of 3,3,5,7,7-penmnitro-Swza-I ,9-nonane diamine In a round-bottom flask fitted with a reflux condenser, 3,3,5,7,7-pentanitro-$-aza-l,9-nonane diisocyanate was heated with a ten-fold excess of nitric acid on a steam bath for a period of 3 hours. The solution was evaporated to dryness in vacuo leaving a quantitative diisocyanate with a dilute aqueous solution of a strong mineral acid, in accordance with the general reaction scheme set forth below:

aN-.A n wsman-.7

Nol no, N

NO: I. 1 70 Jo wherein X, A, and n are asdefined above.

The corresponding free'nitraza di'amines'are generated from the novel mineral acid salts of this invention by neutralizing the salts with inorganic basic salts of alkali Ballistic mortar value l44 yield of the bis-nitric acid salt of 3,3,5,7,7-pentanitro-$ aza-l,9-nonane diamine. Upon recrystallization from concentrated nitric acid the product exhibited a M.P.= of 175-180 C. The elemental analysis of the product is-asfollows:

l The explosive power of this compound was calculated asfollows:'

Lead block value -135 T.N.T.= 100 T.N.T.= 100 As already indicated, a dilute mineral acid is employed for the reaction of the present invention. By dilute acid, as the tennis used herein, is meant an aqueous solution of acid, preferably from about 30 to about 85 concentration. The reaction of this invention is a vigorous one, and I have found that optimum control can be exercisedwhen an acid of about 35% concentration is employed in excess, particularly where the mineral acid used is nitric acid. The excess acid acts as a diluent or solvent, and thereby efiects moderation of the reaction.

The reaction temperature is not critical in the prac: tice of this invention, the only effect of temperature variation being a'corresponding increase or decrease in reaction rate.-, I have found, however, that elevated re- H01! of an impactor time-fuse mechanism firing a action temperatures, such as those from ambient to about 100 0., result in particularly favorable reaction rates, and that the reaction proceeds most eflicaciously at steam bath temperature.

The diisocyanates used as starting materials in this invention are obtained by reacting diacyl halides, such as 6-aza-4,4,6,8,B-pentanitro-l,ll-undecanedioyl chloride, with alkali or alkaline earth metal azides, such as sodium azide, to form the corresponding nitraza azides, and

then heatiiig said nitraza azides to-eifect rearrangement to the desired diisocyanate form. Treating the abovementioned diacyl halide as described results in the formation of 3,3,5,7,7 pentanitro-S-aza 1,9 nonane diiso' cyanate starting materials is more fully described in as-' signees copending US. patent application Serial No.

or alkaline earth metals, such as hydroxides or carbonates, or weak organic acid salts, such as acetates, of alkali or alkaline earth metals. For reasons of convenience and economy, I prefer to use sodium hydroxide as the amine generating agent, but other suitable generating agents, such as calcium hydroxide, magnesium 451,707, filed August 23, 1954, now abandoned. The nitraza diacyl halides are prepared from their correspond-' ing esters, obtained by the condensation of geminal polynitrohydroxy esters in the presence of ammonia or an amine followed by nitration of the condensationproducts, as disclosed in assignees copending application No. 416,382, filed March .15, 1954, now abandoned. The diisocyanates wherein n is greater than 1 are prepared in accordance withthe above procedure by condensing a vhydroxy polynitro ester with the amine, obtained from an isocyanate previously prepared as described, and

3 mblequently forming the acid "halide and reacting it with sodium azide to form the desired isocyanate.

The strong mineral acid with which the diisocyanate is reacted in the practice of this invention is preferably nitric acid or perchloric acid, since when either of these acids is employed, the resulting salt is useful as a high explosive in addition to having utility as an intermediate in the preparation of other high explosive compounds, as delcribed above. However, other strong mineral acids, such as hydrochloric acid, sulfuric acid, or the can be employed for purposes of this invention if desired- It will be appreciated that a wide variety of bis-inorganic acid salts of aliphatic nitraza polynitro diamines can be prepared in accordance with the method of my invention. For example, 2,2,5,8,8-pentanitro-5-aza-l,9- nonane diisocyanate; 2,2,5,'9,9-pentanit;O-5-aza-1,13-mir diisocya'nate; 3 I I 1 l1 diaza-1,l7-heptadecane diisocyanate; and 3,3.5,7 ,7,l0,12. JZ-octanitro-S 1 O-diaza-l, lttetrarlecane diisocyanate react with strong mineral acids, such as nitric acid or perchloric acid, in dilute aqueous solutions, to produce the corresponding mineral acid salts, such as the nittic ncid or perchloric acid salts, of 2,2,fi,8,8-pentanitro-5-.aza 1,9- nonanc diamine; 2,2,5,9,9-pentanitro-5-aza-1,l3rtridccane diarnine; 3,3,6,9,9,l2,l5,IS-OCtanitrWGJZ-diZZa-LU- heptadecane diamine; and 3,3,5,7,7,l0,l2,l2-octanitro 5,l diaza-l,l4-tetradecane diamine, respectively. The free nitraza diamines can be readily generated from these acid salts through neutralization thereof with an inorganicbasic salt or a weak organic acid salt of an alkali ,or alkaline earth metal, as taught herein.

It is apparent that the strong mineral acid salts of my member of this series of aliphatic nitraza polynitro diamines can be obtained by merely reacting the appropri' ate diisocyanate with dilute mineral acid, in accordance with the example ,set forth above. It is equally apparent that the free diarnines can be generated from the mineral acid salts thereof through neutralization with an inorganic basic salt or a weak organic acidcalt of an alkali 01' alkaline earth metal, as taught herein.

This application is a continuation-in-p r of my copending U.S. patent application Serial No. 451,708,1i1ed August 23, 1954, now abandoned.

I claim:

1. As compositions of matter, nitraza compounds selected from the group consisting of aliphatic nit 'g polynitro diamines having the formula:

N03 N01 NO; was Lana AM NO, NO:

110: I NO: NO;

Bal -M. N0: N 01 min the A radicals are lower alkylcnc and an is so sm ll Whole number from 1 to 3. inclusive.

3. As compositions of matter, the strong-mineral acid salts of aliphatic nitraza nolYuitro diaminea having the ten-mule:

wherein X is an anion of a strong mineral acid, A radicals are lower alkylene and n is ,a small whole number from 1 to 3, inclusive.

As p sitions of matter. the blsnitric acid salt LN n of aliphatic nitraza polynitro diamines having the for- N01 L N02 I: wherein the A radicals are lower alkylene and n is a small whole number from 1 to 3, inclusive.

5. As compositions of matter, the bis-perchloric acid salts of aliphatic nitraza polynitro diamines having the tat so. 1.

wherein the A radicals are lower alkylene and n is a small whole number from 1 to 3, inclusive.

6. As a composition of matter, the bis-nitric acid salt of 3,3,5,7,7-pentanitro-5-aza-l,9-nonane diarnine having the structural formula:

7. As a composition of matter, the bis-nitric acid salt of 2,2,5,8,8-pentanitro5-aza-l,9-nonane diamine having the structural formula:

10. As a composition of matter, the bis-nitric acid salt of 3,3,5,7,1,10, 12,l2-octanitro-5,l0-dia;a-1,14-tetradecane dia nine having the structural formula:

ll. The method of preparing a strong mineral acid salt of nitraza compounds selected from the group consisting of aliphatic nitraza polynitro diamines having the formula:

which comprises reacting dilute nitric acid with an aliphatic nitraza polynitro diisocyanate having the formula:

1110: I NO: NO: I OCN-A-C-A-N-A- A.NCO

to, L is. l.

wherein the R radicals are lower alkylene and n is a small whole number from 1 to 3, inclusive.

13. The method of preparing bis-perchloric acid salts of aliphatic nitraza polynitro diamines having the formula:

NO: which comprises reacting dilute perchloric acid with an aliphatic nitraza polynitro diisocyanate having the formula:

l lo: L 3W0: 111

CN-A- 6 17. The method of preparing bis-nitric acid salts of aliphatic nitraza polynitro diamines having the formula:

NO: N0: N0:

-I-A-I!IA- -A-NH:-HNOs which comprises reacting an aliphatic nitraza polynitro diisocyanate having the formula:

NO: I- No: N 0: "I

is, I, I'm. 1.

with 35% nitric acid, in the presence of excess dilute nitric acid and at an elevated temperature; wherein the A radicals are lower alkylene and n is a small whole number from 1 to 3, inclusive.

18. The method of preparing aliphatic nitraza polynitro diamines having the formula:

to. L

which comprises reacting dilute mineral acid with an allphatic nitraza polynitro diisocyanate having the formula:

130. i. No,

wherein the R radicals are lower alkylene and n is a small whole number from 1 to 3, inclusive, to form a bis-mineral acid salt of a diamine and neutralizing the salt with another salt selected from the group consisting of inorganic basic salts of alkali and alkaline earth metals and weak organic acid salts of alkali and alkaline earth metals.

19. The method of preparing the bis-perchloric acid salt of 2,2,5,8,8-pentanitro-5-aza-1,9-nonane diamine, which comprises reacting 2,2,5,8,S-pentanitroJ-aza-l,9- nonane diisocyanate with dilute perchloric acid.

20. The method of claim 17 in which the reaction is conducted at about C.

No references cited. 

1. AS A COMPOSITIONS OF MATTER, NITRAZA COMPOUNDS, SELECTED FROM THE GROUP CONSISTING OF ALIPHATIC NITRAZA POLYNITRO DIAMINES HAVING THE FORMULA: 